Aluminum dual doping and oxygen transport pathway in novel Sr11Mo4−xAlxO23 oxide-ion solid electrolytes

Abstract

Three new electrolytes of composition Sr11Mo4-xAlxO23-δ (x = 0.5, 1.0 and 1.5) were synthesized by wet-chemistry procedures (citrate method) as polycrystalline samples. They were crystallographically studied from synchrotron and neutron diffraction techniques. They derive from the Sr11Mo4O23 complex perovskite, which can be rewritten as Sr1.75□0.25SrMoO5.75, highlighting the relationship with double perovskites A2B′B″O6. From these analyses via Rietveld refinement, a dual doping was found from synchrotron data, where the aluminum is equally allocated at both Sr (B′) and Mo (B″) sites. A detailed analysis of the neutron data from Difference Fourier Maps (DFM) unveiled the oxygen delocalization around the Mo site. From the refined crystal structures at room and high temperatures, a Bond Valence Sum Map (BVSM) analysis was useful to find the oxygen pathway in the crystal structure, and the minimum density to allow connections among oxygen atoms. The structural characterization was complemented with thermogravimetric and thermodilatometric analysis. The ionic conductivity was measured from electrochemical impedance spectroscopy (EIS) in wet and dry air and nitrogen atmospheres.